Calcium beryllium silicate phosphor



April 3, 1951 A. L.. J. SMITH CALCIUM BERYLLIUM SILICATE PHOSPHOR Filed April l2, 1949 ww ogm ATTOFNEY Patented pr. 3, 1951 CALCIUM BERYLLIUM SI-LICATEPHOSPHUR Arthur L. J. Smith'rLancastferg-Pa., assgnorl tot Radio Corporation ofk America,.a corporationv of Delaware.

l Application April'12, 1949*,1S'erial'No'. 86,992v

3.Claims. (C1. 252'-301.4)

This invention relates to a novel luminescent material adapted to emit light within the visible spectrum when subjected to cathode ray excita.-

tion... The-newmaterial may be. described as, a.

manganese activated calcium beryllium" silicate.

Many different types of silicate phosphors haveibeenpreparedin.the. past and some of ythese have been widely used in commerciall apparatus such as television kinescope tubes because; of their excellent.Stability;.high efficiency, and desirable spectral emission characteristics. The novel material of they present invention is a luminescent silicate composition not previously known to have been prepared and which has certain desirableproperties such as unusually long decay time;

One. object of the presentinvention is to provide: a-z novel luminescent. material adapted to emit within. the. visiblercgion: of` the spectrum when excitedi by cathode rays.;

Another object of the invention is to provide a novel cathodoluminescent material having a fairly long decay time.

Another object o-f the invention is to provide Va novel luminescent material characterized by lita The novel material of the invention may be described briefly asbeing a calcium beryllium silicate activated with small amounts of manganese. The material may be further characterized as being a crystalline structure consisting essentially of calcium-beryllium orthosilicate activated with manganese and may incorporate, as solid solutions, large quantitiesof the calcium silicates or beryllium silicate, which may be more simply described as being an excess of silica over the proportion CaO.BeO.SiO2. It may also exist with a slight deficiency of silica, all as more fully explained hereinafter. It should be further understood that the material is not a mere physical mixture of calcium orthosilicate and beryllium orthosilicate but is rather a homogeneous crystal consisting essentially of manganese activated calcium; orthosilicate and. beryllium' orthosilicate in a vsingle lattice structure which:

mayinclude an excess oran deficiency of silica compared with that required by the stoichiomet-` ric ratio CaO.BeO`.SiOz.

A Ymoreexact formula for the novel luminescent material of the' invention may be givenV 'as' (fCaO)y(B'eO) (SiOz) zMn, the zc, y and e stand* ing for molar proportions such that' :c is preferably equal to about 0.25'to71, y is preferably equal.

toaboutvO.25 to 1.6, both ofthese ratiosbeing true when e is equal to 1 and' When'the additional limitation is imposed that ii-if z is not less than about 0.5: nor greater than aboutv 2.11-, The manganese, as is usually the case with activators, is present inrelatively minor amounts. Preferably, the proportion is from about .001 to 0.2 mole in any of the c-ompositions dened above.

Although satisfactory materials may be prepared using any proportion of the constituents as indicated above, the most efcient material has been found to be one having the molar ratios CaO.BeO.SiO2:.01 Mn; that ls, one in which the three principal constituents are present in equimolecular proportions, with the manganese activator being present in the proportion of .01 mole.

The preparation of the novel materials of the present invention is relatively simple. The raw materials must be carefully puried to an exceedingly high degree of purity. rlhey are powdered in a ball mill and thoroughly mixed to obtain homogeneity, then red at a temperature which is preferably about 1250 C. but which may be between l000 and 1500 C. The time of firing may be from 1/2 to 4 hours, a period of about 2 hours being preferred. The ring may take place in air, nitrogen or hydrogen. Firing may also take place in the presence of steam and, if steam is used, the optimum ring time is shortened. The steam appears to act as a catalyst and is especially desirable if the materials are red in an atmosphere of hydrogen.

Calcium chloride may be used as a ux but the firing can readily be accomplished without any flux.

The purified compounds out of which the luminescent material is synthesized are, preferably, the oxides or those compounds which will decompose to form the oxides' under the firing conditions used. Mention may be made of carbonates, nitrates, hydroxides, sulfates, etc. It

g has been found most convenient to use calcium carbonate, manganous carbonate, beryllium oxide, and silicic acid. However, any combinations which, upon reaction during the ring process, form the ultimate required composition may be employed. Thus, for example, even calcium chloride may be used as a medium to introduce calcium provided enough excess silica is used to account for the amount that will be lost through volatilization of silicon-chlorine- (oxygen) compounds. When the chloride is used, firing is best accomplished in an oxidizing atmosphere, but this is not essential.

The manganese activator can be added to the raw material mix as the sulfate, carbonate, iluoride, oxide, nitrate, chloride, etc.

Although the novel material of the invention is preferred in silicate form, it is possible to substitute either germanium or tin for part of the silica. It has been found, for example, that up to .2 of a mole of the silica can be replaced by an equal molar quantity of either germanium dioxide or stannic oxide in any of the compositions.

Depending upon the particular ratio of the constituents selected, the peak wavelength of emission of the material under excitation by cathode ray bombardment varies somewhat. For the preferred composition containing equal molecular ratios of CaO. BeO and S102, the peak wavelength is about 5700 and this shifts toward the red wavelengths as the `CaO-i-BeO S102 molar ratio approaches vone or less. The maximum amount of the shift brought about in this manner is about 500 Angstroms with the molar ratio 2CaO.BeO.3SiO2. A complete spectral emission curve withinv the visible spectrum for 2,457,054

the material CaO.BeO.SiOz:.01 Mn is shown in the figure. The data were taken at ordinary room temperature of about 72 F.

There has thus been described a novel luminescent material adapted to be excited by electron bombardment. The material is characterized by rather long decay time, thus making it especially suitable for such practical applications as radar tube screens although its decay time is not too long for use in many other types of cathode ray tube apparatus. It, also, has relatively high eiciency of emission and good stability under the usual conditions of use, as well as the added advantage of ease of preparation.

I claim as my invention:

1. A luminescent material having the general formula 3:(CaO) y BeO)z(SiOz) :Mn where .1: is 0.25-1 and y is 0.25-1.6 when a is 1, where the molar ratio it l REFERENCES CITED The following references are of record inthe file of this patent:

UNITED. STATES PATENTS Number Name Date 2,049,765 Fischer Aug. 4, 1936 2,118,091 Leverenz May 24, 1938 Leverenz Dec. 21, 1948 

1. A LUMINESCENT MATERIAL HAVING THE GENERAL FORMULA X(CAO)Y(BEO)Z(SIO2):MN WHERE X IS 0.25-1 AND Y IS 0.25-1.6 WHEN Z IS 1, WHERE THE MOLAR RATIO 